Dichloropyridyl methyl cyanamidines

ABSTRACT

Novel dichloropyridylmethylcyanamidines of the formula  
                 
in which 
         R 1  represents hydrogen, alkyl or optionally substituted aralkyl and    R 2  represents hydrogen, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted aryl, optionally substituted aryloxy or optionally substituted arylthio, a process for preparing the novel compounds and their use for controlling unwanted microorganisms.

The present invention relates to novel dichloropyridylmethylcyanamidines, to a process for their preparation and to their use for controlling unwanted microorganisms.

It is already known that certain dichloropyridyl derivatives have microbicidal and in particular fungicidal properties (cf. EP-A 0 334 813, EP-A 0 334 809, EP-A 0 334 812, EP-A 0 332 579, EP-A 0 288 976, JP-A 87-242 393 and DE-A 2 620 781). The activity of these substances is good; however, at low application rates it is sometimes unsatisfactory.

This invention now provides novel dichloropyridylmethylcyanamidines of the formula

in which

-   R¹ represents hydrogen, alkyl or optionally substituted aralkyl and -   R² represents hydrogen, optionally substituted alkyl, optionally     substituted alkoxy, optionally substituted alkylthio, optionally     substituted aryl, optionally substituted aryloxy or optionally     substituted arylthio.

Furthermore, it has been found that dichloropyridylmethylcyanamidines of the formula (I) can be prepared by reacting dichloropyridylmethylamines of the formula

in which

-   R¹ is as defined above,     with cyanimines of the formula     in which -   R² is as defined above and -   X represents in each case optionally substituted alkoxy, alkylthio,     aryloxy or arylthio,     if appropriate in the presence of a diluent.

Finally, it has been found that the dichloropyridylmethylcyanamidines of the formula (I) have very good microbicidal properties and can be used both in crop protection and in the protection of materials for controlling unwanted microorganisms. The compounds according to the invention can not only be used for the direct control of unwanted microorganisms but also have resistance-inducing action on plants.

Surprisingly, the dichloropyridylmethylcyanamidines of the formula (I) according to the invention have considerably better fungicidal activity than the constitutionally most similar prior-art compounds of the same direction of action.

The formula (I) provides a general definition of the dichloropyridylmethylcyanamidines according to the invention. Preference is given to those compounds of the formula (I) in which

-   R¹ represents hydrogen, alkyl having 1 to 4 carbon atoms or aralkyl     having 6 to 10 carbon atoms in the aryl moiety and 1 to 4 carbon     atoms in the alkyl moiety and -   R² represents hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy     having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms,     aryl having 6 to 10 carbon atoms, aryloxy having 6 to 10 carbon     atoms or arylthio having 6 to 10 carbon atoms, where the three last     mentioned radicals may each be mono- to trisubstituted by identical     or different substituents from the group consisting of fluorine,     chlorine, bromine and alkyl having 1 to 4 carbon atoms.

Particular preference is given to those compounds of the formula (I) in which

-   R¹ represents hydrogen, methyl, ethyl or benzyl and -   R² represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or     t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy,     methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or     t-butylthio, or represents phenyl, phenoxy or phenylthio, where the     three last mentioned radicals may each be mono- to trisubstituted by     identical or different substituents from the group consisting of     fluorine, chlorine, bromine, methyl and ethyl.

Using (2,6-dichloro-4-pyridinyl)methylamine and methyl cyanimidoformate as starting materials, the course of the process according to the invention can be illustrated by the formula scheme below.

The formula (II) provides a general definition of the dichloropyridylmethylamines required as starting materials for carrying out the process according to the invention. In this formula, R¹ preferably has those meanings which have already been mentioned in connection with the description of the compounds of the formula (I) according to the invention as being preferred for this radical.

The dichloropyridylmethylamines of the formula (II) are known or can be prepared by known methods (cf. Rec. Trav. Chim. Pays-Bas 52 (1933), 55-56).

The formula (III) provides a general definition of the cyanimines furthermore required as starting materials for carying out the process according to the invention. In this formula, R² preferably has those meanings which have already been mentioned in connection with the description of the compounds of the formula (I) according to the invention as being preferred for this radical. X preferably represents alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, phenoxy or phenylthio, where the two last mentioned radicals may be mono- to trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, methyl and ethyl.

If R² represents hydrogen, optionally substituted alkyl or optionally substituted aryl, X particularly preferably represents methoxy or methylthio.

If R² represents optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted aryloxy or optionally substituted arylthio, X preferably has those meanings which have already been mentioned above as being preferred. With particular preference, the radicals R² and X are identical.

The cyanimines of the formula (III) are known or can be prepared by known processes (cf. J. Org. Chem. 28 (1983), 1816-1821, Synthesis 1971, 263 and Arch. Pharm. 303 (1970), 625-633).

Suitable diluents for carrying out the process according to the invention are all customary inert organic solvents. Preference is given to using aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decaline; halogenated hydrocarbons, such as, for example, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane, ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofliran, 1,2-dimethoxy ethane, 1,2-diethoxy ethane or anisole; ketones, such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; esters such as methyl acetate or ethyl acetate; sulfoxides, such as dimethyl sulfoxide; sulfones, such as sulfolane; alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether.

When carrying out the process according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the process is carried out at temperatures between 0° C. and 120° C., preferably at temperatures between 0° C. and 80° C.

The process according to the invention is generally carried out under atmospheric pressure. However, it is also possible to operate under reduced or elevated pressure, for example under pressures between 0.1 bar and 10 bar.

When carrying out the process according to the invention, in general from 0.5 to 2.0 mol, preferably from 0.8 to 1.5 mol, of cyanimine of the formula (III) are employed per mole of dichloropyridylmethylamine of the formula (II). Work-up is carried out by customary methods.

The compounds according to the invention have potent microbicidal activity and can be employed for controlling unwanted microorganisms, such as fungi and bacteria, in crop protection and in the protection of materials.

Fungicides can be employed in crop protection for controlling Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

Bactericides can be employed in crop protection for controlling Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.

Some pathogens causing fungal and bacterial diseases which come under the generic names listed above may be mentioned as examples, but not by way of limitation:

-   Xanthomonas species, such as, for example, Xanthomonas campestris     pv. oryzae; -   Pseudomonas species, such as, for example, Pseudomonas syringae pv.     lachrymans; -   Erwinia species, such as, for example, Erwinia amylovora; -   Pythium species, such as, for example, Pythium ultimum; -   Phytophthora species, such as, for example, Phytophthora infestans; -   Pseudoperonospora species, such as, for example, Pseudoperonospora     humuli or Pseudoperonospora cubensis; -   Plasmopara species, such as, for example, Plasmopara viticola; -   Bremia species, such as, for example, Bremia lactucae; -   Peronospora species, such as, for example, Peronospora pisi or P.     brassicae; -   Erysiphe species, such as, for example, Erysiphe graminis; -   Sphaerotheca species, such as, for example, Sphaerotheca fuliginea; -   Podosphaera species, such as, for example, Podosphaera leucotricha; -   Venturia species, such as, for example, Venturia inaequalis; -   Pyrenophora species, such as, for example, Pyrenophora teres or P.     graminea (conidia form: Drechslera, syn: Helminthosporium); -   Cochliobolus species, such as, for example, Cochhobolus sativus     (conidia form: Drechslera, syn: Helminthosporium); -   Uromyces species, such as, for example, Uromyces appendiculatus; -   Puccinia species, such as, for example, Puccinia recondita; -   Sclerotinia species, such as, for example, Sclerotinia sclerotiorum; -   Tilletia species, such as, for example, Tilletia caries; -   Ustilago species, such as, for example, Ustilago nuda or Ustilago     avenae; -   Pellicularia species, such as, for example, Pellicularia sasakii; -   Pyricularia species, such as, for example, Pyricularia oryzae; -   Fusarium species, such as, for example, Fusarium cuhnorum; -   Botrytis species, such as, for example, Botrytis cinerea; -   Septoria species, such as, for example, Septoria nodorum; -   Leptosphaeria species, such as, for example, Leptosphaeria nodorum; -   Cercospora species, such as, for example, Cercospora canescens; -   Altemaria species, such as, for example, Altemaria brassicae; and -   Pseudocercosporella species, such as, for example,     Pseudocercosporella herpotrichoides.

The fact that the active compounds, in the concentrations required for controlling plant diseases, are tolerated well by plants permits the treatment of above-ground parts of plants, of propagation material and seeds and of the soil.

The active compounds according to the invention can be used with particularly good results for controlling cereal diseases, such as, for example, against Erysiphe species.

The active compounds according to the invention also show a strong invigorating action in plants. Accordingly, they are suitable for mobilizing the internal defences of the plant against attack by unwanted microorganisms.

In the present context, plant-invigorating (resistance-inducing) compounds are to be understood as meaning substances which are capable of stimulating the defence system of plants such that, when the treated plants are subsequently inoculated with unwanted microorganisms, they display substantial resistance to these microorganisms.

In the present case, unwanted microorganisms are to be understood as meaning phytopathogenic fungi, bacteria and viruses. The compounds according to the invention can thus be used to protect plants within a certain period of time after treatment against attack by the pathogens mentioned. The period of time for which this protection is achieved generally extends for 1 to 10 days, preferably 1 to 7 days, from the treatment of the plants with the active compounds.

The active compounds according to the invention are also suitable for increasing the yield of crops. In addition, they show reduced toxicity and are well tolerated by plants.

If appropriate, the active compounds according to the invention can, at certain concentrations and application rates, also be employed as herbicides, for regulating plant growth and for controlling animal pests. If appropriate, they can also be used as intermediates or precursors in the synthesis of other active compounds.

According to the invention, it is possible to treat all plants and parts of plants. Plants are to be understood here as meaning all plants and plant populations,.such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including plant cultivars which can or cannot be protected by plant breeders' certificates. Parts of plants are to be understood as meaning all above-ground and below-ground parts and organs of plants, such as shoot, leaf, flower and root, examples which may be mentioned being leaves, needles, stems, trunks, flowers, fruit-bodies, fruits and seeds and also roots, tubers and rhizomes. Parts of plants also include harvested material and vegetative and generative propagation material, for example seedlings, tubers, rhizomes, cuttings and seeds.

The treatment of the plants and parts of plants according to the invention with the active compounds is carried out directly or by action on their environment, habitat or storage area according to customary treatment methods, for example by dipping, spraying, evaporating, atomizing, broadcasting, brushing-on and, in the case of propagation material, in particular in the case of seeds, furthermore by one- or multilayer coating.

In the protection of materials, the compounds according to the invention can be employed for protecting industrial materials against infection with, and destruction by, unwanted microorganisms.

Industrial materials in the present context are understood as meaning non-living materials which have been prepared for use in industry. For example, industrial materials which are intended to be protected by active compounds according to the invention from microbial change or destruction can be tackifiers, sizes, paper and board, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials which can be infected with, or destroyed by, microorganisms. Parts of production plants, for example cooling-water circuits, which may be impaired by the proliferation of microorganisms may also be mentioned within the scope of the materials to be protected. Industrial materials which may be mentioned within the scope of the present invention are preferably tackifiers, sizes, paper and board, leather, wood, paints, cooling lubricants and heat-transfer liquids, particularly preferably wood.

Microorganisms capable of degrading or changing the industrial materials which may be mentioned are, for example, bacteria, fungi, yeasts, algae and slime organisms. The active compounds according to the invention preferably act against fungi, in particular molds, wood-discoloring and wood-destroying fungi (Basidiomycetes) and against slime organisms and algae.

Microorganisms of the following genera may be mentioned as examples:

-   Alternaria, such as Alternaria tenuis, -   Aspergillus, such as Aspergillus niger, -   Chaetomium, such as Chaetomium globosum, -   Coniophora, such as Coniophora puetana, -   Lentinus, such as Lentinus tigrinus, -   Penicillium, such as Penicillium glaucum, -   Polyporus, such as Polyporus versicolor, -   Aureobasidium, such as Aureobasidium pullulans, -   Sclerophoma, such as Sclerophoma pityophila, -   Trichoderma, such as Trichoderma viride, -   Escherichia, such as Escherichia coli, -   Pseudomonas, such as Pseudomonas aeruginosa, and -   Staphylococcus, such as Staphylococcus aureus.

Depending on their particular physical and/or chemical properties, the active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and microencapsulations in polymeric substances and in coating compositions for seeds, and ULV cool and warm fogging formulations.

These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents, liquefied gases under pressure, and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants, and/or foam formers. If the extender used is water, it is also possible to employ, for example, organic solvents as auxiliary solvents. Essentially, suitable liquid solvents are: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide or dimethyl sulfoxide, or else water. Liquefied gaseous extenders or carriers are to be understood as meaning liquids which are gaseous at standard temperature and under atmospheric pressure, for example aerosol propellants such as halogenated hydrocarbons, or else butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: for example ground natural minerals. such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as finely divided silica, alumina and silicates. Suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, or else synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks. Suitable emulsifiers and/or foam formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates, or else protein hydrolysates. Suitable dispersants are: for example lignosulfite waste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Other possible additives are mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can, as such or in their formulations, also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, to broaden, for example, the activity spectrum or to prevent development of resistance. In many cases, synergistic effects are obtained, i.e. the activity of the mixture is greater than the activity of the individual components.

Suitable mixing components are, for example, the following compounds:

Fungicides:

-   aldimorph, ampropylfos, ampropylfos-potassium, andoprim, anilazine,     azaconazole, azoxystrobin, -   benalaxyl, benodanil, benomyl, benzamacril, benzamacryl-isobutyl,     bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S,     bromuconazole, bupirimate, buthiobate, -   calcium polysulfide, capsimycin, captafol, captan, carbendazim,     carboxin, carvon, quinomethionate, chlobenthiazone, chlorfenazole,     chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon,     cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram,     carpropamid, -   debacarb, dichlorophen, diclobutrazole, diclofluanid, diclomezine,     dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph,     diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione,     ditalimfos, dithianon, dodemorph, dodine, drazoxolon, -   edifenphos, epoxiconazole, etaconazole, ethirimol, etridiazole, -   famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram,     fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate,     fentin hydroxide, ferbam, ferimzone, fluazinam, flumetover,     fluoromide, fluquinconazole, flurprimidol, flusilazole,     flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium,     fosetyl-sodium, fthalide, fuberidazole, furalaxyl, furametpyr,     furcarbonil, furconazole, furconazole-cis, furmecyclox, fenhexamid, -   guazatine, -   hexachlorobenzene, hexaconazole, hymexazole, -   imazalil, imibenconazole, iminoctadine, iminoctadine albesilate,     iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (IBP),     iprodione, inimamycin, isoprothiolane, isovaledione, iprovalicarb, -   kasugamycin, kresoxim-methyl, copper preparations, such as: copper     hydroxide, copper naphthenate, copper oxychloride, copper sulfate,     copper oxide, oxine-copper and Bordeaux mixture, -   mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil,     metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram,     metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin, -   nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, -   ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim,     oxyfenthiin, -   paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen,     pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz,     procynudone, propamocarb, propanosine-sodium, propiconazole,     propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon,     pyroxyfur, -   quinconazole, quintozene (PCNB), quinoxyfen, -   sulfur and sulfur preparations, spiroxamine, -   tebuconazole, tecloftalam, tecnazene, tetcyclacis, tetraconazole,     thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram,     tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol,     triazbutil, triazoxide, trichlamide, tricyclazole, tridemorph,     triflumizole, triforine, triticonazole, trifloxystrobin, -   uniconazole, -   validamycin A, vinclozolin, viniconazole, -   zarilarnide, zineb, ziram and also -   Dagger G, -   OK-8705, -   OK-8801, -   α-(1,1-dimethylethyl)-β-(2-phenoxyethyl)-1H-1,2,4-triazole-1-ethanol, -   α-(2,4-dichlorophenyl)-β-fluoro-b-propyl-1H-1,2,4-triazole-1-ethanol, -   α-(2,4-dichlorophenyl)-β-methoxy-a-methyl-1H-1,2,4-triazole-1-ethanol, -   α-(5-methyl-1,3-dioxan-5-yl)-β-[[4-(trifluoromethyl)-phenyl]-methylene]-1H-1,2,4-triazole-1-ethanol, -   (5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(1H-1,2,4-triazol-1-yl)-3-octanone, -   (E)-a-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide, -   1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-ethanone-O-(phenylnethyl)-oxime, -   1-(2-methyl-1-naphthalenyl)-1H-pyrrol-2,5-dione, -   1-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidindione, -   1-[(diiodomethyl)-sulfonyl]-4-methyl-benzene, -   1-[[2-(2,4dichlorophenyl)-1,3-dioxolan-2-yl]-methyl]-1H-imidazole, -   1-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-1H-1,2,4-triazole, -   1-[1-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-1H-imidazole, -   1-methyl-5-nonyl-2-(phenylmethyl)-3-pyrrolidinole, -   2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide, -   2,6-dichloro-5-(methylthio)-4-pyrimidinyl-thiocyanate, -   2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide, -   2,6-dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzanide, -   2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole, -   2-[(1-methylethyl)-sulfonyl]-5-(trichloromethyl)-1,3,4-thiadiazole, -   2-[[6-deoxy-4-O-(4-O-methyl-β-D-glycopyranosyl)-a-D-glucopyranosyl]-amino]-4-methoxy-1H-pyrrolo[2,3-d]pyrimidine-5-carbonitrile, -   2-aminobutane, -   2-bromo-2-(bromomethyl)-pentanedinitrile, -   2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide, -   2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamide, -   2-phenylphenol (OPP), -   3,4-dichloro-1-[4-(difluoromethoxy)-phenyl]-1H-pyrrol-2,5-dione, -   3,5-dichloro-N-[cyano[(1-methyl-2-propynyl)-oxy]-methyl]-benzamide, -   3-(1,1-dimethylpropyl-1-oxo-1H-indene-2-carbonitrile, -   3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine, -   4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulfonamide, -   4-methyl-tetrazolo[1,5-a]quinazolin-5(4H)-one, -   8-hydroxyquinoline sulfate, -   9H-xanthene-2-[(phenylamino)-carbonyl]-9-carboxylic hydrazide, -   bis-(1-methylethyi)-3-methyl-4-[(3-methylbenzoyl)-oxy]-2,5-thiophenedicarboxylate, -   cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol, -   cis-4-[3-[4-(1,1-dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethyl-morpholine     hydrochloride, -   ethyl [(4-chlorophenyl)-azo]-cyanoacetate, -   potassium bicarbonate, -   methanetetrathiol-sodium salt, -   methyl     1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate, -   methyl N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate, -   methyl N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate, -   N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-acetamide, -   N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thlienyl)-acetamide, -   N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitro-benzenesulfonamide, -   N-(4-cyclohexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine, -   N-(4-hexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine, -   N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)-acetamide, -   N-(6-methoxy)-3-pyridinyl-cyclopropanecarboxamide, -   N-[2,2,2-trichloro-1-[(chloroacetyl)-amino]-ethyl]-benzamide, -   N-[3-chloro-4,5-bis(2-propinyloxy)-phenyl]-N′-methoxy-methanimidamide, -   N-formyl-N-hydroxy-DL-alanine-sodium salt, -   O,O-diethyl     [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate, -   O-methyl S-phenyl phenylpropylphosphoramidothioate, -   S-methyl 1,2,3-benzothiadiazole-7-carbothioate, -   spiro[2H]-1-benzopyrane-2,1′(3′H)-isobenzofuran]-3′-one,     Bactericides: -   bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,     kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin,     probenazole, streptomycin, tecloftalam, copper sulfate and other     copper preparations.     Insecticides/Acaricides/Nematicides: -   abamectin, acephate, acetamiprid, acrinathrin, alanycarb, aldicarb,     aldoxycarb, alpha-cypermethrin, alphamethrin, amitraz, avermectin,     AZ 60541, azadirachtin, azamethiphos, azinphos A, azinphos M,     azocyclotin, -   Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus     thuringiensis, baculoviruses, Beauveria bassiana, Beauveria tenella,     bendiocarb, benfuracarb, bensultap, benzoximate, betacyfluthrin,     bifenazate, bifenthrin, bioethanomethrin, biopermethrin, BPMC,     bromophos A, bufencarb, buprofezin, butathiofos, butocarboxim,     butylpyridaben, -   cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan,     cartap, chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos,     chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M,     chlovaporthrin, cis-resmethrin, cispermethrin, clocythrin,     cloethocarb, clofentezine, cyanophos, cycloprene, cycloprothrin,     cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine, -   deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron,     diazinon, dichlorvos, diflubenzuron, dimethoate, dimethylvinphos,     diofenolan, disulfoton, docusat-sodium, dofenapyn, -   eflusilanate, emamectin, empenthrin, endosulfan, Entomopfthora spp.,     esfenvalerate, ethiofencarb, ethion, ethoprophos, etofenprox,     etoxazole, etrimfos, -   fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion,     fenothiocarb, fenoxacrim, fenoxycarb, fenpropathrin, fenpyrad,     fenpyrithrin, fenpyroximate, fenvalerate, fipronil, fluazuron,     flubrocythrinate, flucycloxuron, flucythrinate, flufenoxuron,     flutenzine, fluvalinate, fonophos, fosmethilan, fosthiazate,     fubfenprox, furathiocarb, -   granulosis viruses, -   halofenozide, HCH, heptenophos, hexaflumuron, hexythiazox,     hydroprene, -   imidacloprid, isazofos, isofenphos, isoxathion, ivermectin, -   nuclear polyhedrosis viruses, -   lambda-cyhalothrin, lufenuron, -   malathion, mecarbam, metaldehyde, methamidophos, Metharhizium     anisopliae, metharhizium flavoviride, methidathion, methiocarb,     methomyl, methoxyfenozide, metolcarb, metoxadiazone, mevinphos,     milbemectin, monocrotophos, -   naled, nitenpyram, nithiazine, novaluron, -   omethoate, oxamyl, oxydemethon M, -   Paecilomyces fumosoroseus, parathion A, parathion M, permethrin,     phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim,     pirimicarb, pirimiphos A, pirimiphos M, profenofos, promecarb,     propoxur, prothiofos, prothoate, pymetrozine, pyraclofos,     pyresmethrin, pyrethrum, pyridaben, pyridathion, pyrimidifen,     pyriproxyfen, -   quinalphos, -   ribavirin, -   salithion, sebufos, silafluofen, spinosad, sulfotep, sulprofos, -   tau-fluvahnate, tebufenozide, tebufenpyrad, tebupirimiphos,     teflubenzuron, tefluthrin, temephos, temivinphos, terbufos,     tetrachlorvinphos, theta-cypermethrin, thiamethoxam, thiapronil,     thiatriphos, thiocyclam hydrogen oxalate, thiodicarb, thiofanox,     thuringiensin, tralocythrin, tralomethrin, triarathene, triazamate,     triazophos, triazuron, trichlophenidine, trichlorfon, triflumuron,     trimethacarb, thiacloprid, -   vamidothion, vaniliprole, Verticillium lecanii, -   YI 5302, -   zeta-cypermethrin, zolaprofos, -   (1R-cis)-[5-(phenylnethyl)-3-furanyl]-methyl-3-[(dihydro-2-oxo-3(2H)-furanylidene)-methyl]-2,2-dimethylcyclopropanecarboxylate, -   (3-phenoxyphenyl)-methyl-2,2,3,3-tetramethylcyclopropanecarboxylate, -   1-[(2-chloro-5-thiazolyl)methyl]tetrahydro-3,5-dimethyl-N-nitro-1,3,5-triazine-2(1H)-imine, -   2-(2-chloro-6-fluorophenyl)-4-[4-(1,1-dimethylethyl)phenyl]-4,5-dihydro-oxazole, -   2-(acetyloxy)-3-dodecyl-1,4-naphthalenedione, -   2-chloro-N-[[[4-(1-phenylethoxy)-phenyl]-amino]-carbonyl]-benzamide, -   2-chloro-N-[[[4-(2,2-dichloro-1,1-difluoroethoxy)-phenyl]-amino]-carbonyl]-benzamide, -   3-methylphenyl propylcarbamate, -   4-[4-(4-ethoxyphenyl)-4-methylpentyl]-1-fluoro-2-phenoxy-benzene, -   4-chloro-2-(1,1-dirnethylethyl)-5-[[2-(2,6-dimethyl-4-phenoxyphenoxy)ethyl]thio]-3(2H)-pyridazinone, -   4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy]-3(2H)-pyridazinone, -   4-chloro-5-[(6-chloro-3-pyridinyl)methoxy]-2-(3,4-dichlorophenyl)-3(2H)-pyridazinone, -   Bacillus thuringiensis strain EG-2348, -   [2-benzoyl-1-(1,1-dimethylethyl)-hydrazinobenzoic acid, -   2,2-dimethyl-3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro[4.5]dec-3-en-4-yl     butanoate, -   [3-[(6-chloro-3-pyridinyl)methyl]-2-thiazolidinylidene]-cyanamide, -   dihydro-2-(nitromethylene)-2H-1,3-thiazine-3(4H)-carboxaldehyde, -   ethyl     [2-[[1,6-dihydro-6-oxo-1-(phenylmethyl)-4-pyridazinyl]oxy]ethyl]-carbamate, -   N-(3,4,4-trifluoro-1-oxo-3-butenyl)-glycine, -   N-(4-chlorophenyl)-3-[4-(difluoromethoxy)phenyl]-4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide, -   N-[(2-chloro-5-thiazolyl)methyl]-N′-methyl-N″-nitro-guanidine, -   N-methyl-N′-(1-methyl-2-propenyl)-1,2-hydrazinedicarbothioamide, -   N-methyl-N′-2-propenyl-1,2-hydrazinedicarbothioamide, -   O,O-diethyl-[2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate,

A mixture with other known active compounds, such as herbicides, or with fertilizers and growth regulators, is also possible.

In addition, the compounds of the formula (I) according to the invention also have very good antimycotic activity. They have a very broad antimycotic activity spectrum in particular against dermatophytes and yeasts, molds and diphasic fungi (for example against Candida species such as Candida albicans, Candida glabrata) and Epidermophyton floccosum, Aspergillus species such as Aspergillus niger and Aspergillus fumigatus, Trichophyton species such as Trichophyton mentagrophytes, Microsporon species such as Microsporon canis and audouinii. The list of these fungi does by no means limit the mycotic spectrum which can be covered, but is only for illustration.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. Application is carried out in a customary manner, for example by watering, spraying, atomizing, broadcasting, dusting, foaming, spreading, etc. It is furthermore possible to apply the active compounds by the ultra-low volume method, or to inject the active compound preparation or the active compound itself into the soil. It is also possible to treat the seeds of the plants.

When using the active compounds according to the invention as fungicides, the application rates can be varied within a relatively wide range, depending on the kind of application. For the treatment of parts of plants, the active compound application rates are generally between 0.1 and 10,000 g/ha, preferably between 10 and 1000 g/ha. For seed dressing, the active compound application rates are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. For the treatment of the soil, the active compound application rates are generally between 0.1 and 10,000 g/ha, preferably between 1 and 5,000 g/ha.

The compositions used for protecting industrial materials generally comprise the active compounds in an amount of from 1 to 95% by weight, preferably from 10 to 75% by weight.

The use concentrations of the active compounds according to the invention depend on the type and the occurrence of the microorganisms to be controlled and on the composition of the material to be protected. The optimum application rate can be determined by test series. In general, the use concentrations are in the range from 0.001 to 5% by weight, preferably from 0.05 to 1.0% by weight, based on the material to be protected.

The activity and the activity spectrum of the active compounds to be used according to the invention in the protection of materials or of the compositions, concentrates or quite generally formulations preparable therefrom can be increased by adding, if appropriate, further antimicrobial compounds, fingicides, bactericides, herbicides, insecticides or other active compounds for widening the activity spectrum or to obtain special effects, such as, for example, additional protection against insects. These mixtures may have a wider activity spectrum than the compounds according to the invention.

As already mentioned above, it is possible to treat all plants and their parts according to the invention. In a preferred embodiment, wild plant species and plant cultivars, or those obtained by conventional biological breeding, such as crossing or protoplast fusion, and parts thereof, are treated. In a fur ther preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof, are treated. The term “parts” or “parts of plants” or “plant parts” has been explained above.

According to the invention particular preference is given to treating plants of the plant cultivars which are commercially available or in use.

Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also result in superadditive (“synergistic”) effects. Thus, for example, reduced application rates and/or a widening of the activity spectrum and/or an increase in the activity of the substances and compositions which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, better quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products are possible which exceed the effects which were actually to be expected.

The transgenic plants or plant cultivars (i.e. those obtained by genetic engineering) which are preferably to be treated according to the invention include all plants which, in the genetic modification, received genetic material which imparted particularly advantageous useful properties (“traits”) to these plants. Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, better quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products. Further and particularly emphasized examples of such properties are a better defence of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and/or viruses, and also increased tolerance of the plants to certain herbicidally active compounds. Examples of transgenic plants which may be mentioned are the important crop plants, such as cereals (wheat, rice), corn, soya beans, potatoes, cotton, oilseed rape and also fruit plants (with the fruits apples, pears, citrus fruits and grapes), and particular emphasis is given to corn, soya beans, potatoes, cotton, and oilseed rape. Traits that are emphasized are in particular increased defence of the plants against insects by toxins formed in the plants, in particular those formed in the plants by the genetic material from Bacillus thuringiensis (for example by the genes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CryIF and also combinations thereof) (hereinbelow referred to as “Bt plants”). Traits that are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (for example the “PAT” gene). The genes which impart the desired traits in question can also be present in combination with one another in the transgenic plants. Examples of “Bt plants” which may be mentioned are corn varieties, cotton varieties, soya bean varieties and potato varieties which are sold under the trade names YIELD GARD® (for example corn, cotton, soya beans), KnockOut® (for example corn), StarLink® (for example com), Bollgard® (cotton), Nucoton® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants which may be mentioned are corn varieties, cotton varieties and soya bean varieties which are sold under the trade names Roundup Ready® (tolerance to glyphosate, for example corn, cotton, soya bean), Liberty Link® (tolerance to phosphinotricin, for example oilseed rape), IMI® (tolerance to imidazolinones) and STS® (tolerance to sulfonylureas, for example corn). Herbicide-resistant plants (plants bred in a conventional manner for herbicide tolerance) which may be mentioned also include the varieties sold under the name Clearfield® (for example corn). Of course, these statements also apply to plant cultivars which have these genetic traits or genetic traits still to be developed, and which will be developed and/or marketed in the future.

The plants listed can be treated according to the invention in a particularly advantageous manner with the compounds of the general formula (I) or the active compound mixtures according to the invention. The preferred ranges stated above for the active compounds or mixtures also apply to the treatment of these plants. Particular emphasis is given to the treatment of plants with the compounds or mixtures specifically mentioned in the present text.

The preparation and the use of the active compounds according to the invention is illustrated by the examples below.

PREPARATION EXAMPLES Example 1

3.13 g (10 mMol) of (2,6-dichloro-4-pyridyl)methylamine are dissolved in 20 ml of methanol, and 0.89 g (10 mMol) of methyl cyanimidoformate is added. The reaction mixture is stirred at room temperature for 12 hours and then concentrated under reduced pressure. The oily residue is stirred with petroleum ether, giving a crystalline product. This is filtered off with suction and air-dried. This gives 1.92 g (84% of theory) of N′-cyano-N-[(2,6-dichloro-4-pyridinyl)methyl]imidoformamide of melting point 160° C.

The compounds of the formula (I) according to the invention listed in Table 1 below are likewise prepared by the methods given above. TABLE 1 (I)

Ex. No. R¹ R² m.p. (° C.) 2 —H —O-phenyl 188 3 —H —C₂H₅ 184 4 —H —CH₃ 196 5 —H —S—CH₃ 248 6 —H n-propyl 105 7 —H —S—C₂H₅ 198 8 —H —S—CH₂—CH₂—CH₃ 167 9 —H —S—CH(CH₃)₂ 189 10 —H phenyl 183

USE EXAMPLES Example A

Erysiphe-Test (Barley)/Induction of Resistance Solvent: 48.8 parts by weight of N,N-dimethylformamide Emulsifier:  1.2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for resistance-inducing activity, young cereal plants are sprayed with the preparation of active compound at the stated application rate. 4 days after the treatment, the plants are inoculated with spores of Erysiphe graminis f. sp. hordei. The plants are then placed in the greenhouse at 70% relative atmospheric humidity and a temperature of 18 C.

Evaluation is carried out 7 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.

Active compounds, application rates and test results are shown in the table below. TABLE A Erysiphe-Test (barley)/induction of resistance Application rate of active compound in Efficacy Active compound g/ha in % According to the invention:

750 80

750 100 

750 95 

1. A dichloropyridylmethylcyanamidine of the formula

in which R¹ represents hydrogen, alkyl or optionally substituted aralkyl and R² represents hydrogen, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted aryl, optionally substituted aryloxy or optionally substituted arylthio.
 2. A dichloropyridylmethylcyanamidine of the formula (I) as claimed in claim 1 in which R¹ represents hydrogen, alkyl having 1 to 4 carbon atoms or aralkyl having 6 to 10 carbon atoms in the aryl moiety and 1 to 4 carbon atoms in the alkyl moiety and R² represents hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, aryl having 6 to 10 carbon atoms, aryloxy having 6 to 10 carbon atoms or arylthio having 6 to 10 carbon atoms, where the three last mentioned radicals may each be mono- to trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine and alkyl having 1 to 4 carbon atoms.
 3. A dichloropyridylmethylcyanamidine of formula (I) as claimed in claim 1 in which R¹ represents hydrogen, methyl, ethyl or benzyl and R² represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, or represents phenyl, phenoxy or phenylthio, where the three last mentioned radicals may each be mono- to trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, methyl and ethyl.
 4. A dichloropyridylmethylcyanamidine as claimed in claim 1, wherein said dichloropyridylmethylcyanamidine is represented by the formula


5. A dichloropyridylmethylcyanamidine as claimed in claim 1, wherein said dichloropridylmethylcyanamidine is represented by the formula


6. A dichloropyridylmethylcyanamidine as claimed in claim 1, wherein said dichloropyridylmethylcyanamidine is represented by the formula


7. A dichloropyridylmethylcyanamidine as claimed in claim 1, wherein said dichloropyridylmethylcyanamidine is represented by the formula


8. A process for preparing a dichloropyridylmethylcyanamides of the formula (I) as claimed in claim 1, comprising: reacting a dichloropyridylmethylamines of the formula

in which R¹ is as defined above in claim 1, with a cyanimine of the formula

in which R² is as defined in claim 1 and X represents in each case optionally substituted alkoxy, alkylthio, aryloxy or arylthio, optionally in the presence of a diluent.
 9. A composition for controlling unwanted microorganisms, comprising at least one dichloropyridylmethylcyanamidine of the formula (I) as claimed in claim 1, and one or more extenders and/or surfactants.
 10. (Cancelled)
 11. A method for controlling unwanted microorganisms, comprising applying a dichloropyridylmethylcyanamidines of the formula (I) as claimed in claim 1 to the microorganisms and/or their habitat.
 12. A process for preparing a composition for controlling unwanted microorganisms, comprising mixing a dichloropyridylmethylcyanamidines of formula (I) with one or more extenders and/or surfactants. 